Azo compounds of the thiophanthraquinone series



Patented July'lO,f195 1 I E UNITED STATES PATENT OFFICE AZO COMPOUNDS F THETBIOPHANTHRA- QUINONE SERIES Herman Schroeder and Lorraine' A. Ringros'e, Wilmington, DeL, assignors to E; I. du Pont de Nemours & compan Wilmington, Del., a corporati'on of Delaware N0 Drawing. Application June 17, 1949, Serial No. 99,874

7 Claims. (Cl. 260-152) This invention relates to the preparation of the group consisting of OH, -Nl-I2, C1 and new dye intermediates of the thiophanthra- O-alkyl in which the alkyl radical contains quinone series, and more particularly to new from 1 to 18 carbon atoms. These compounds azobiphenylcarbonylaminothiophanthraquinone which contain the free carboxylic acid radical or compounds. 5 functional derivative thereof may, on further While a nu ber o at y s in th yel ow ra e condensation either directly or after a simple have been used in e dyeing a d p t g of teX- hydrolysis step, be converted to a wide range of tiles, the fastness properties of these yellow new and valuable vat dyes. colors are poor as compared with the fastness The compounds of the above given formula properties of many of the other colors in the vat may be prepared in good yields and in an exye C ass. Wher ye low y s in th Class W t cellent state of purity by the condensation of one improved fastness properties have been found, ml of an aminothiophanthraquinone compound they in turn are either dull or weak tinctorially with one molof 4,4-azobiphenyl-4,4-dicarand therefore the various yellow dyes in the vat bonyl" chloride. The reaction is preferably cardy lass ar chos n to a sw r a parti ular n d. ried out in an inert solvent under anhydrous conbalancing the question of fastness, brightness and ditions at temperatures of from 140 to 200 C.

cost of the particular dye available. i The condensation appears to take place sub- It is an object of this invention toproduce new stantially quantitatively on one end of the'diand valuable dye intermediates particularly usee carbonylchloride only, for, by its analysis andits ful as acylating agents in the manufacture of further condensation with amines, the produ'ct yellow vat dyes of desirable shades; It-isa further appears to be uniform in its composition and to object of the invention to produce new azobibe asubstantially pure compound. I phenylcarbonylaminothiophanthraquinone com The following examples are given to illustrate pounds which on further condensation-or ring the invention. The partsused are'by weight; closure yield valuable yellow vat dyes which'ex Example 1 hibit exceptionally good tinctorial strength and light fastness properties and which are valuable A mixture of 420 parts of dry nitrobenz ene and for the printing as well as the dyeing of textile 28 parts of azobiphenyldicarbonyl chloride was fibers. heated to 130 G am l then 14.7 parts of 5-amino-j The compounds of this invention are 4,4-azo'- 30 thiophanthraquinone were added. The charge biphenyl 4 carbonylaminothiophanthraquiwas heated at 1'50 C. for one hour, cooled to 100 none-4-carboxylic acids and their functional Ci, filtered and the bright yellow filter cake was derivatives which may be represented by the genwashed with nitrobenzene, benzene and petroleum eral formula: v ether, in turn, and dried.

H o o in which R stands for a thiophanthraquinone An analysis of the product substantiates the radical which may be unsubstituted or it may formula:

contain simple monovalent substituents such as It is obtained in practically quantitative yield. halogen, methoxy, benzoylamino and th'enoyl The yield and product obtainable on further reamino groups, which thiophanthraquinone r'a'diactionwith amines indicates that there is no ap: cal is attached to the imino group through its; preciable amount of diamide formed in the first benzene nucleus, and X stands for a member of reaction.

Example 2 A mixture of 80 parts of dry nitrobenzene and o S H parts of azobiphenyldicarbonyl chloride was treated with 3 parts of 2-chloro-5-aminothiophanthraquinone according to the procedure given in Example 1. The bright yellow product which was isolated in excellent yield is reprequinone were added to a mixture or" 60 parts of 4 Example 1. The greenish-yellow product has the formula:

y-QQ- -QQW Example 6 A mixture of 90 parts of dry nitrobenzene and 6 parts of azobiphenyldicarbonyl chloride was treated with 3.1 parts of 8-aminothiophanthraquinone according to the procedure given in Ex- The bright yellow crystalline product obtained in excellent yield is represented by the sented by the formula: ample o l s o1' Example 3 At p rts of 6-aminothiophanthraformula:

H o H o NC- v :1

Any of the acid chloride compounds of this dry ortho-dichlorobenzene and 4 parts of azobiinvention which may be produced as illustrated phenyldicarbonyl chloride. The charge was heated at 150 C. for one hour, and the product was isolated by the method given previously in Example 1. The greenish-yellow crystalline product, obtained in excellent yield, is represented by the formula:

Example 4 in the above examples may be converted to the acid amide by treating the reaction mass in which it is formed, and without isolation, with ammonia at temperatures of around 125 C. for 3 to 4 hours. The resulting acid amides may be recovered by filtering and washing with benzene,

55 alcohol and hot water, in turn, or in the same manner as illustrated in the above examples for the acid chloride compounds.

Example 7 Ten (10) parts of the condensation product of 1 mol of 6-amino-5-chlorothiophanthraquinone and 1 mol of azobiphenyldicarbonyl Example 5 A mixture of 4.45 parts of azobiphenyldicarbonyl chloride in '75 parts of dry m'trobenzene was treated with 3.2 parts of fi-amino-l-bromothichloride, as prepared in the above examples, were added to 200 parts of nitrobenzene and the whole was heated to 130 C. At this temperature ammonia gas was bubbled through the mass for 4 hours. The amide so formed was filtered off,

ophanthraquinone according to the method in washed free from nitrobenzene with alcohol, and

then with hot water. It dyes cotton in weak may be substitutedfor the methyl alcohol, such as yellow shades from a brownish alkaline hydroethyl, isopropyl, butyl, isobutyl, octyl, cetyl, dosulfite vat. It has the formula: decyl and octadecyl alcohol, etc. These alcohols The acid chloride compounds of this invention may be primary or secondary alcohols. These may'also be readily converted to compounds conesters may also be hydrolyzed to the free acid taining the free carboxylic acid group by dissolv- 1 by the usual hydrolysis method.

ing the acid chloride compound in concentrated The acid chlorides, free acids, amides and esters sulfuric acid at from 5 to C. This effects hyare vattable and, where they contain halogen in y s of the acid chloride gr p W liberation a position ortho to the thiophanthraquinone of hydrochloric acid. Alternatively, the free acid imino group, they may be converted by ring closcompounds may be prepared as follows: ureto the oxazole ring into valuable dyes, as more Example 8 particularly disclosed in our copending application Serial No. 99,875 filed of even date herewith.

T0 the H t O W913 Cake, Containing 50 Other aminothiophanthraquinones than those Parts Of the Condensation Product O 1 o of 6- specifically used in the examples to illustrate the ami o-5-ch o t p a q With 1 11101 invention may of course be employed, such as the of azobiphenylcarbonyl chloride (as obtained in 5,7-dibromo 6 aminothiophanthraquinon 7- y f h a v x pl 200 p r f ni r aminothiophanthl'aquinone, 5-amino-8-meth0xybenzene were added. After heating to 130 C., 25 thiophanthraquinone, 8-amino-5-benzoylaminoparts of water were added under reflux condenser thiophanthraquinone, 8-amino-5-thenoylaminoand heating was continued at 110-l30 C. for four 0 thiophanthraquinone. These may be substituted hours. A sample of the reaction mass was rein the specific examples to give dye intermediates moved. It was filtered, washed with nitrobenzene coming within the scope of the present invenand alcohol and dried. It was difiicult to vat but tion.

dyed cottom from a brownish vat in weak yellow 3 In place of pure aminothiophanthraquinones,

shades. It has the formula: 5 the normally occurring mixtures of the 5- and 8- o 01 ll NHOO N=N 000B The mono acid chloride compounds of the pres- (alpha) or the 6- and 7-(beta) -amines may be ent invention may be converted to esters by reemployed. Similarly, a mixture of 5-chloro-6- acting with alcohols of from 1 to 18 carbon atoms, aminothiophanthraquinone with S-chloro-I- preferably in an organic solvent at temperatures aminothiophanthraquinone and other similar of from 125 to 135 C'., as illustrated in the folmixtures may be used to give valuable dye interlownig example: mediates of this series. Of the halogenated Example 9 Q amines, those possessing halogen in a position ortho to the amino group are particularly val- Ten (10) parts of the condensation product of uable for further condensations and ring forma- 1 mol of 6-amino-5-chlorothiophanthraquinone tions,

with 1 mol of azobiphenyldicarbonyl chloride were The condensation employed in the production suspended in 200 parts of nitrobenzene and the of th compounds of thi invention n'lay be whole heated to 130 C. in a vessel fitted with recarried out under a. wide variety of conditions as flux condenser. Nine (9) parts of methyl alcohol to; temperature and. time, depending upon the rewere gradually added at this temperature, and a actants to be used. A temperature range of temperature of 110-130 C. was maintained for l40-200 C. usually gives most satisfactory six hours. The product was filtered oil after 0 results, although temperatures outside of this cooling, washed with nitrobenzene and alcohol, range are occasionally necessary. The condensafinally steamed, and dried. It was a light yellow tions are carried out in inert organic solvents compound Which dyed cotton in Weak yellow such asthe aromatic hydrocarbons, and chlorinshades from a brownish alkaline hydrosulfite ated and nitrated aromatic hydrocarbons; catavat. It has the formula: lysts such as pyridine may be used. It is usually In the above example, other aliphatic alcohols preferable tov add the amine to the'acid chloride of the series containing from 1 to 18 carbon atoms y at reaction temperatureor to: heat up an equimolar mixture of the two. The acid chloride itself may be used, or if it appears preferable it may be prepared in situ, e. g. by treating the acid with thionyl chloride in solvent, removing the excess of thionyl chloride by air blowing, and proceeding with the condensation as described in the above examples. obtained are surprisingly stable crystalline compounds Which may be isolated in high yield.

Compounds of the present invention are new products which on further condensation give novel and particularly valuable vat dyestuffs of very good light fastness and good printing properties. They are of particular utility for the preparation of unsymmetrical vat dyestuffs of outstanding properties, as more particularly described in our co-pending applications Serial Nos. 99,876, 99,877, and 99,878. r The 4,4-azobiphenyldicarboxylic acid employed in the above examples is readily prepared by the sodium hydroxide-glucose reduction of 4,4'-nitrophenyl benzoic acid. The dicarboxylic acid is converted to the acid chloride by treating The acid chlorides thus 8 The nitro-ortho 2 thenoyl) benzoic acids used in the preparation of the above aminothiophanthraquinones may be prepared iii-good yields and purity by the processes more particularly described in the Lee and Weinmayr application Serial No. 723,670, filed January 22, 1947, now UQS. Patent No. 2,513,573. The nitro-substituted phthalic anhydride may be reacted with the Grignard reagent prepared from, 2-bromothe free acid or its sodum salt with thionyl chloride, or phosphorus pentachloride in an inert solvent such as aromatic hydrocarbons or the chlorinated or nitrated aromatic hydrocarbons. The azobiphenyldicarbonyl chloride employed in the above examples is the 4,4'-azobiphenyl- 4,4'-dicarbonyl chloride which has a melting point of 260-262 C.

The aminothiophanthraquinones employed as the starting materials for the production of the compounds of this invention may be prepared by the processes more particularly described in the co-pending application of Lee and Weinmayr, Serial No. 723,672, filed January 22, 1947, now U. S. Patent No. 2,501,132. The 5-aminothiophanthraquinone (having a melting poirit of 231-232 C.) is preferably prepared from either the 3- or S-amino-ortho-(Z-thenoyl)-benzoic acids (or mixtures of the same) by efiecting ring closure in 10 parts of 96% to 100% sulfuric acid at temperatures of from 125 to 140 C. The 7-aminothiophanthraquinone, having a melting point of 274-275 C., is prepared in a similar manner from either the 4- or 5-amino-ortho-(2- thenoyl) -benzoic acids, or mixtures of the same.

The 6-aminothiophanthraquinone (having a melting'point of 271 C.) is preferably prepared by the ring closure of either the 4- or 5-nitroortho-(2-thenoyl) -benzoic acids (or mixtures of the same) with substantially 100% sulfuric acid at temperatures of from 70 to 160 C., with subsequent reduction of the nitro group. The ring closure may, if desired, be carried out in from one to ten minutes by maintaining the temperature thiophene or 2-iodothiophene, or they may be prepared by condensing the nitrophthalic anhydride with thiophene by the usual Friedel- Crafts synthesis with the aid of aluminum chloride or similar condensing agent. The l-nitro-2-(2-thenoyl) benzoic acid is readily obtained in good yield by reacting thiophene with 2-carbomethoxy-5-nitrobenzoyl chloride in nitrobenzene in the presence of aluminum chloride, followed by hydrolysis of the ester to the nitrothenoyl benzoic acids.

duced from the corresponding nitrophthalic anhydrides by carrying out the esterification in an inert organic diluent which has a boiling point above 170 C., but which exhibits negligible solvent action on the monomethyl ester such as nitrobenzene or the chlorobenzenes, at 20 to 40 C., using from 1 to 1.1 mol proportions of methanol. Certain of these nitrothenoyl benzoic acid methyl esters are disclosed and claimed in co-pending application of Gladding, Serial No. 71,203, filed January 15, 1949, now U. 6. Patent No. 2,519,040. Where the amino ortho (2 thenoyl) -benzoic acid is desired, the corresponding nitro compound may be reduced to the amine either in caustic solutions with zinc or iron or v by means of hydrogen in the presence of a nickel catalyst. I r

The halogen aminothiophanthraquinones employed may be prepared by reacting aminothiophanthraquinones with chloride or bromine and, where necessary, eliminating part of the halogen in the polyhalogenaminothiophanthraquinones, as more particularly described in our co-pending and now abandoned application Serial No. 99,879.

The aminobenzoylaminothiophanthraquinones or the aminothenoylaminothiophanthraquinones which may be employed in the production of the compounds of this invention may be produced from the aminohalogen compounds .by first benzoylating or thenoylating by the usual methods, then condensing with paratoluene sulionamide and hydrolyzing the toluene sulfonamlde group to give the free amine.

We claim:

1. The compounds of the general formula:

at 120 to 160 C. where from 97% to 100% sulfuric acid is employed. The nitro group may be reduced to the amine with sodium hydrosulfite in sodium hydroxide solution. The 8- aminothiophanthraquinone (having a melting point of 235236 C.) may be prepared in the same manner from the 3-nitroor the 6nitroortho-(2-thenoyl)-benzoic acids, or mixtures of the same. The nitro-substituted thiophanthraquinones are more particularly disclosed and claimed in an application of Lee and Weinmayr, Serial No; 723,671, filed January 22, 1947, now U. '8. Patent No. 2,501,131.

in which R stands for a thiophanthraquinone radical of the group consisting of the unsubstituted thiophanthraquinone radical and the thiophanthraquinone radicals carrying monovalent substituents of the. group consisting ,of bromine,

J -chlorine, methoxy, b'enzoylamino and thenoyl- The 2-carbomethoxy-3- (and 5)-nitrobenzoic acids are preferably pro- 1 2. The compounds of the formula:

i S H w r in which the thiophanthraquinone radical is atin which the thiophanthraquinone radical is attached to the imino group in an alpha position tached to the imino group through its benzene on its benzene ring. nucleus and Y stands for halogen of the group 3. The compounds of the formula: consisting of bromide and chlorine attached on CfiO OQ- QQ in which the thiophanthraquinone radical is atthe benzene ring in a position ortho to the imino tached to the imino group in a beta position on 25 group. its benzene ring. 5. The compound of the formula:

4. The compounds of the formula:

i S H 0 6. The compound of the formula:

7. The compound of the formula:

ii-Og HERMAN E. SCHROEDER. LORRAINE A. RING-ROSE.

No references cited.

Certificate of Correction Patent No. 2,559,670 July 10, 1951 HERMAN E. SOHROEDER ET AL.

It is hereby certified that error appears the printed specification of the above numbered patent requiring correctlon as follows:

Column 3, Example 2, for that portion of the formula reading 0 o s C] s 01 read column 5, line 34, for cottom read cotton; lines 48 and 49, for follownig read following; column 8, line 73, for 0H read NH column 10, line 4;, for bromide read bromine;

and that the said Letters Patent should be read as corrected above, so that the same may conform to the record of the case in the Patent Oflice.

Signed and sealed this 9th day of October, A. D. 1951.

THOMAS F. MURPHY,

Assistant Commissioner of Patents. 

1. THE COMPOUNDS OF THE GENERAL FORMULA: IN WHICH R STANDS FOR A THIOPHANTHRAUINONEE RADICAL OF THE GROUP CONSISTING OF THE UNSUBSTITUTED THIOPHANTHRAQUINONE RADICAL AND THE THIOPHANTHRAQUINONE RADICALS CARRYING MONOVALENT SUBSTITUENTS OF THE GROUP CONSISTING OF BROMINE, CHLORINE, METHOXY, BENZOYLAMINO AND THENOYLAMINO GROUPS, WHICH THIOPHANTHRAQUINONE RADICAL IS ATTACHED TO THE IMINO GROUP THROUGH ITS BENZENE NUCLEUS, AND X STANDS FOR A MEMBER OF THE GROUP CONSISTING OF -OH, OH2, -CL AND -O-ALKYL IN WHICH THE ALKYL RADICAL CONTAINS FROM 1 TO 18 CARBON ATOMS. 